Organo-mercury dicarboxylate microbicides



ure ia-3mg Patented Oct. 19, 1954 UNIT] 3 amazon ORGAN O -1\IERCURY DICARBOXYLATE MICROBICIDES Milton Nowak, Union, N. J., assignor to Nuodex Products 00., Inc., Elizabeth, N. 5., a corporation of New York No Drawing. Application July 8, 1952, Serial No. 297,771

12 Claims. 1

preservation of lumber and cellulosic materials,

and as microbicides in therapeutic uses.

In all of the aforementioned applications it is highly desirable that the organo-mercury compound employed possess a very high order of microbicidal efiicacy for three primary reasons, namely, (1) the more effective the compound the more economical its use to attain a desired level of activity, (2) the lower the percentage of the compound employed the less the toxicity hazard, and, (3) the lower the percentage of the compound employed, the less likelihood of undesirable side effects and reactions.

The organo-mercury compounds of this invention have proven particularly effective when employed in coating compositions to inhibit and premmmew i. vent the groWthoi micro-orgahisms on a surface paintedwith compositions containing statem- 'poiifids.'l aint ed surfaces are subject to severe and damaging attack by many fungi, more especially, those of the genera Pullularia, Alternaria, Cylinclrocephalum, P h o m a, Cephalosporiurn, Stemphylium, Trichotheciurn, Aspergillus and Penicillium.

Mildew discoloration and deterioration of paint films is well recognized in the southern areas of the United States and in the tropics. This phenomenon also occurs in temperate and even northern climates wherever adequate moisture and humidity are present to support the growth of fungi. It is difiicult to estimate the enormous monetary loss occasioned by the necessity of re painting surfaces which have deteriorated or become unsightly due to fungal attack. The use of organc-mercury compounds to prevent growth of mildew on painted surfaces has become widespread and there has been an ever increasing demand for products of this kind which will be more and more effective when used in minimum amounts.

As a result of prolonged experimentation and research, I have discovered and proven by conelusive tests that an unusually highly eflicient performance results from the employment of the mercurials of the present invention which comprise compounds having the general formula:

wherein R and R is each an organic residue, such as an aryl, alkyl, aralkyl or alicyclic group linked directly to a mercury atom through a carbon atom, and wherein R and R may be the same or different from one another, and where R" is a carbon atom chain of at least five carbon atoms, substituted or unsubstituted, saturated or unsaturated.

The following examples are illustrative of preferred forms of the present invention:

Example I Di-(phenylmercury) dodecenyl succinate, a compound of the formula RHgOOCCH2--CHR"COOHR' where R and R are phenyl and R" is dodecenyl.

266 grams of dodecenyl succinic anhydride (derived from the condensation of triisobutylene and maleic anhydride),

588 grams of phenylmercury hydroxide, and

3200 grams of naphtha (The naphtha used is a solvent commonly used in the paint industry and is characterized by a flash point of F. (Tag closed cup), a boiling range of 315-350 F.

and a kauri butanol value of 94.)

are introduced into a suitable flask fitted with an agitator. An exothermic reaction results on agitation of this mixture. The reaction is brought to completion by heating at 180 F. for one-half hour.

7 The water formed during the reaction is removed in vacuo and the solution is then filtered through clay. This solution now consists of di- (phenylmercury) dodecenyl succinate in naphtha, containing 10% mercury by weight. It is miscible with Xylol, toluol, benzol, mineral spirits, linseed oil and soybean oil.

This compound was incorporated in a paint to yield a concentration of .0025% mercury and the paint was then subjected to the following test procedure:

No. 30 Whatman filter paper or equivalent was given two coats of paint on one side, the sheet being brushed uniformly in all directions to assure a uniform impregnation. Sufficient time was allowed for the first coat to become tackfree prior to applying the second coat. After drying for 48 hours, half of the paint impregnated samples were subjected to a leaching test in running water. The water had a DH of 6.5-7.5 and flowed at a rate of approximately 8 liters per hour. The sheets were then cut into 1 inch squares. i

A sterile culture medium was prepared from 30 grams of malt extract, grams of agar and 1000 cc. of distilled water, and a number of 10 cm. diameter Petri dishes were each filled with 35 cc. of the medium.

Approximately 1.25 cc. of an inoculum consisting of a suspension of Pullularia pullulans was distributed over the surface of the hardened culture medium. The five replicated test specimens were dipped in boiling water and then laid firmly on the center of the inoculated culture medium. 0.25 cc. of the inoculum was then placed on the test specimen.

The inoculated plates were incubated at 28-30 C. and a relative humidity of 80415 72, for four weeks, after which they were examined.

At the same time identical treatment was carried out with the same paint base, but using, instead of di-(phenyl-mercury) dodecenyl succinate, phenyl mercury naphthenate which is considered in the trade as a very excellent mildew-proofing agent. Simultaneously phenyl mercury naphthenate tests were carried out using twice as much of such naphthenate, namely, 005% mercury in the paint. At the conclusion of these tests, the di- (phenylmercury) dodecenyl succinate treated samples showed no growth whatsoever. As a matter of fact in the unleached samples, a definite zone of inhibition was present on the petri dish surfaces. In contradistinction all test samples utilizing the phenylmercury naphthenate showed some growth on the unleached samples and moderate to heavy growth on the leached samples.

The foregoing tests demonstrated very definitely the high degree of excellence of the particular compound here tested. Similar tests were carried out with the compounds of several of the other examples, hereinafter given, and the results also indicated the high degree of effectiveness of these compounds as microbicides.

Example II Di-(tolylmercury) dodecenyl succinate, a compound of the formula RHgOOCCHzCHR"-COOHgR' where R. and R are tolyl and R" is dodecenyl.

284 grams of dodecenyl succinic acid (wherein the dodecenyl group is a straight chain containing one double bond or unsaturated linkage) 616 grams of tolyl mercury hydroxide, and

2000 grams of benzene are introduced into a suitable flask fitted with an agitator, reflux condenser and thermometer. An exothermic reaction results. The reaction is completed on heating at 160 F. for one-half hour. Under reduced pressure the water formed during the reaction and the benzene solvent are removed by distillation. The residue in the flask consists of di-(tolylmercury) dodecenyl succinate, an amber solid containing 46.2% mercury. This compound is soluble in toluene, turpentine, xylol, mineral spirits and linseed oil.

0.1% of this compound was dissolved in a xylol solution containing 6% paraffin wax. The resulting solution proved to be an effective waterproofing and mildewproofing treatment for canvas awnings, chair seats, umbrellas, rope, etc.

4 Example III Di-(chlorophenylmercury) octenyl succinate, a compound of the formula where R, and R'-'-are chlorophenyl and R is octenyl.

656 grams of chlorophenylmercury hydroxide, 210 grams of octenyl succinic anhydride, and 2100 grams of toluene are introduced into a suitable flask fitted with a stirrer. The mixture is agitated and heated at F. for one hour until the reaction is completed. The water of reaction is removed in vacuo. Upon addition of more toluene to bring the total to 4000 grams of solution, a 10% mercury solution of di-(chlorophenylmercury) octenyl succinate is now obtained. This amber solution is miscible with xylene, turpentine, mineral spirits, soybean oil and chlorobenzene.

Example IV Di-(naphthylmercury) decenyl succinate, a compound of the formula RHgOOCCH2-CHR' 'COOHgR where R- and R are naphthyl and R" is decenyl.

688 grams of naphthyl mercury hydroxide, 238 grams of decenyl succinic anhydride, and, 2100 grams of benzene are placed in a flask fitted with a stirrer and reflux condenser and heated at reflux for 45 minutes. At that time all of the naphthyl mercury hydroxide will have reacted. On distilling off the water of reaction and the solvent under reduced pressure, a tan powder containing 4.4% mercury is obtained. This compound, di-(naphthylmercury) decenyl succinate, is soluble in naphtha, toluene, mineral spirits and linseed oil.

Example V Phenylmercury, tolylmercury decenyl succinate, a compound of the formula RHgOOC-CH2-CHR' '-COOHgR wherein R is phenyl, R is tolyl and R is decenyl.

294 grams of phenylmercury hydroxide, 308 grams of tolylmercury hydroxide, 256 grams of decenyl succinic acid, and 2500 grams of toluene are placed in a suitable flask fitted with an agitator. An exothermic reaction ensues and is brought to completion by heating at F. for one hour. The water of reaction is removed under vacuo and the solution is filtered through clay. On the addition of more toluene to bring the total weight of the solution to 4,000 grams, a solution of phenylmercury tolylmercury decenyl succinate, containing 10% mercury is obtained. This dark red solution is miscible with mineral spirits, benzene, turpentine, soya modified alkyd resins and linseed oil.

Example VI Chlorophenylmercury, t butylphenylmercury, gamma-phenylallyl succinate, a compound of the formula RHgOOCCHz-CHR' 'COOHgR' where R, is chlorophenyl, R is t-butylphenyl and R" is gamma-phenylallyl.

328 grams of chlorophenylmercury hydroxide, 350 grams t-butylphenylmercury hydride,

234 grams of gamma-phenylallylsuccinic acid, and 2000 grams of benzene were placed in a flask fitted with a stirrer. An exothermic reaction resulted. Comoletion of the reaction. was brought about by refluxing for 90 minutes with rapid agitaton. On distilling oil the Water of reaction and solvent, there is obtained an amber pasty solid consisting of 45.6% mercury. This compound, chlorophenylmercury, tbutylphenylmercury, gamma-phenylallyl succinate, is soluble in toluene, butyl benzene, turpentine, linseed oil and xylol.

Example VII Di- (ethylmercury) dodecenyl succinate, a com-- pound of the general formula RHgOOC-CHzCI-IR' '-COOHgR' wherein R and R are ethyl and R" is dodecenyl.

492 grams of ethylmercury hydroxide, 260 grams of dodecenyl succinic anhydride, and 2000 grams of mineral spirits Di(noctylmercury) tetradecenyl succinate, a compound of the formula wherein R and R are octyl and R" is tetradecenyl.

660 grams n-octylmercury hydroxide, 312 grams of tetradecenyl succinic acid, and 1500 grams of benzene are placed in a flask fitted with a reflux condenser. The reaction is completed by refluxing for three hours. The Water of reaction and solvent are removed under vaouo. A reddish amber solid, the di-(n-octy1mercury) tetradecenyl succinate, containing 42.7% mercury, remains. It is soluble in petroleum ether, mineral spirits, linseed oil and xylol.

Example IX t-Butylphenylmercury, tolylmercury dodecenyl succinate, a compound of the formula wherein R is t-butylphenyl, R, is tolyl and R" is dodecenyl.

350 grams of t-butylphenylmercury hydroxide, 308 grams of tolylrnercury hydroxide,

284 grams of dodecenyl succinic acid, and 2000 grams of naphtha are placed in a flask tted with a stirrer. The reaction is brought to completion under the same conditions as in Example I. On addition of sol vent to make up 4,000 grams total, an amber solu tion of t-butylphenyl mercury, tolyl mercury, dodecenyl succinate in naphtha containing of mercury is obtained. This solution is miscible with benzene, toluene, mineral spirits, soybean oil and turpentine.

r K a Example X Di-(phenylmeroury) octyl' succinate, a compound of the formula RHgOOCCI-Iz-CHR-COOHR' wherein R and R are phenyl and R" is octyl.

588 grams of phenylmercury hydroxide, 212 grams of octyl succinic anhydride, and 1500 grams of benzene are heated under reflux for one hour in a flask fitted with a reflux condenser. The water of re-- action and the solvent are removed in vacuo. Di-(phenylmercury) octyl succinate, a brown crystalline solid containing 51.2% mercury remains. This compound is soluble in petroleum ether, toluene, turpentine and linseed oil.

Example XI Di-(cyclohcxylmercury) octenyl succinate, a compound of the formula wherein R and R are cyclchexyl and R" is octenyl.

600 grams of cyclohexylmercury hydroxide, 210 grams of octenyl succinic acid, and 2300 grams of toluene are placed in a flask fitted with an eiflcient stirrer. Agitation and heating at F. are continued for three hours until the reaction is brought to completion. After drying with 30 grams of anhydrous clay and filtering and upon adding toluene to make up a total of 8,000 grams, a 5% mercury solution of di-(cyclohexylmercury) octenyl succinate is obtained. This solution is miscible with turpentine, mineral spirits, linseed oil and xylol.

Example XII Di- (phenylmercury) decenyl succinate, a compound of the formula RHgOOCCHz-CHR"-COOHgR' wherein R and R are phenyl and R," is decenyl.

588 grams of phenylmercury hydroxide, 238 grams of decenyl succinic anhydride, and, 1800 grams of turpentine are placed in a flask fitted with a stirrer. An exothermic reaction results. Reaction is brought to completion by heating at F. for 20 minutes with agitation. reaction and some solvent are removed and the solution is filtered through a clay bed. On adding turpentine to make up a total of 2660 grams, a 15% mercury solution of di-(phenylmercury) decenyl succinate is obtained. This pale amber solution is miscible with soybean oil, xylol, benzene, mineral spirits and toluene.

Example XIII Di-(phenylmercury) octenyl succinate, a compound or" the formula Rl-IgOOCCH2-CHR --COOHgR' wherein R and R are phenyl and R is octenyl.

538 grams of phenylmercury hydroxide,

210 grams of octenyl succinic anhydride, and 2000 grams of benzene are placed in a flask fitted with a stirrer and reflux condenser. An exothermic reaction re-- sults. The reaction is brought to completion by heating under reflux for 30 minutes with agita- Under vacuo the water or" tion. The solution is then filtered through absorptive clay to remove the water of reaction and impurities. Under vacuo the solvent is removed and an amber pasty'solid containing 51.3% mercury remains. This compound, di-(phenylmercury) octenyl succinate, is soluble in petroleum ether, acetone, turpentine and linseed oil.

Example XIV Di-(phenylmercury) tetradecenyl succinate, a compound of the formula wherein R and R are phenyl and R is tetradecenyl.

588 grams of phenylmercury hydroxide, 294 grams of tetradecenyl succinic anhydride, and 2200 grams of naphtha are placed in a fiask fitted with a stirrer. Reaction is brought about by heating at 165 F. for 90 minutes with agitation. The resulting solution is partially distilled under vacuo to remove the water of formation. Upon filtration and addition of naphtha to make 4,000 grams, a. 10% mercury solution of di-(phenylmercury) tetradecenyl succinate is obtained. This dark red solution is miscible with turpentine, soybean oil, xylol, and mineral spirits.

Example XV Di-(phenylmercury) hexadecenyl succinate, a compound of the formula wherein R and R are phenyl and R is hexadecenyl.

588 grams of phenylmercury hydroxide, 322 grams of hexadecenyl succinic anhydride, and 2400 grams of t-butyl benzene are placed in a flask fitted with a stirrer. Reaction is brought about by heating at 180 F. for 90 minutes with agitation. Under vacuo the water of reaction is removed. With the addition of more t-butyl benzene to make up a total of 4,000 grams, a 10% mercury solution of di- (phenylmercury) hexadecenyl succinate is obtained. This amber solution is miscible with turpentine, linseed oil, xylol, benzene and mineral spirits.

It will be apparent from the foregoing description that it is possible to prepare compounds of this invention having a wide range of solubility characteristics for specific purposes. It should be further noted that the compounds of this invention are especially effective for the purposes stated and permit of the employment of a very small percentage of the compounds in relatively large dilutions for the protective purposes indicated.

The aforementioned compounds have proven to be effective fungicides and microbicides not only in paints, but in the preservation of leather, wood, textiles, casein solutions, and cellulosic materials in general.

In my Patent No. 2,423,044, issued June 19-17, I disclosed the employment of a succinic acid salt of a polymercurated compound and I make no claim for this particular compound in this application. However, experience has shown that the compounds of this invention are far superior in performance to the succinic compound of my said prior patent. I am not prepared to state the reasons for the vast difference in performance, but experience has shown it to be so. The two compositions are chemically differentiated by reference to the fact that the compounds of this invention are salts of mercury compounds wherein only one mercury atom is present in the grouping which is attached to each carboxylic acid group, whereas in the compound of my prior patent, the di-carboxylic acid was employed to form a salt of two or more mercury atoms which were attached to a single aryl group.

Having thus fully described the invention, what I claim as new and desire to secure by Letters Patent is:

1. A new oil soluble compound having the formula RHgOOCCH2-CHR"-COOI-IgR', wherein R and R are selected from the group consisting of alkyl, aryl, alkaryl, ohloraryl, and alicyclic radicals, and wherein Rmnts a hydrocarbon chain of not less than 5 carbon atoms.

2. A new compound according to claim 1, wherein R and R are aryl.

3. A new compound according to claim 1, wherein R and R are aryl and R is aliphatic and contains not less than 5 carbon atoms.

4. A new compound according to claim .1, wherein R and R are phenyl groups and R is aliphatic and contains not less than 5 carbon atoms.

5. A new compound according to claim 1, wherein R and R are aryl and R" is a dodecenyl group.

6. A new compound according to claim 1, wherein R and R are phenyl groups and R" is a dodecenyl group.

7. A new compound according to claim 1, wherein R and R are phenyl groups and R is a decenyl group.

8. A new compound according to claim 1, wherein R and R are phenyl groups and R is a tetradecenyl group.

9. A new compound according to claim 1, wherein R and R are phenyl groups and R is a hexadecenyl group.

10. A new compound according to claim 1, wherein R and R are phenyl groups and R is an octenyl group.

11. A coating composition containing a minor amount of the compound of claim 1.

12. A coating composition containing a minor amount of the compound of claim 1, wherein R and R are phenyl groups and R is a dodecenyl group.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,118,033 Anderson May 24, 1938 2,360,426 Kyrides Oct. 17, 1944 2,381,852 Hochwalt Aug. '7, 1945 2,423,044 Nowak June 24, 1947 

1. A NEW OIL SOLUBLE COMPOUND HAVING THE FORMULA RHGOOC-CH2-CHR"-COOHGR'', WHEREIN R AND R'' ARE SELECTED FROM THE GROUP CONSISTING OF ALKYL, ARYL, ALKARYL, CHLORARYL, AND ALICYCLIC RADICALS, AND WHEREIN R" REPRESENTS A HYDROCARBON CHAIN OF NOT LESS THAN 5 CARBON ATOMS.
 11. A COATING COMPOSITION CONTAINING A MINOR AMOUNT OF THE COMPOUND OF CLAIM
 1. 